Process for forming optical sound track

ABSTRACT

A process for forming an optical sound track which comprises applying a nitrogen containing heterocyclic compound in which at least one of the nitrogen atoms is connected to a group having 6 or more carbon atoms to form a quaternary salt to a sound track area of a multilayer color photographic material, after color development but prior to a bleaching step, whereby an optical sound track can be easily prepared on a conventional multilayer color photographic material.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for forming sound images on acolor photographic material and, more particularly, to a process forforming an optical sound track on a multilayer color photographicmaterial.

2. Description of the Prior Art

In general, there are two types of processes for recording sound imageson a color photographic material for use in the field of motion picturesor television: one is an optical sound-recording system and the other isa magnet sound-recording system. The present invention relates to aprocess for forming sound tracks suitable for use in the opticalsound-recording system.

The reproduction of sound by an optical sound-recording system in acolor print film, a color reversal film, a color reversal print film,etc. as is used in the field of motion pictures or television isaccomplished by the steps of converting a sound signal recorded on afilm as a variation in density or area to a light signal, converting thelight signal to an electrical signal by means of a light acceptor andthen converting the electrical signal to a sound signal. In suchreproduction steps, photoelectric tubes having various spectralcharacteristics are used as a light acceptor. Of these, the one usedmost universally is designated S-1 type, which has a spectralsensitivity maximum in the infrared region at about 800 mμ (see, forexample, Adrin Cornwell Clyne, Color Cinematography, page 593 (1951)).

On the other hand, in conventional color photographic materials based ona subtractive color process, the main absorption of the dyes formed bythe coupling reaction between an oxidation product of a color developingagent, such as a p-phenylenediamine, and a color coupler is always in aregion of the visible spectrum, which absorption therefore does notcoincide with the spectral characteristics of the abovedescribedphotoelectric tube. These color dye images provide, therefore, a soundoutput which is too weak to be practical. Consequently, in recordingsound on a color photographic material, usually a processing step whichforms silver images or silver sulfide on a sound track is carried out,and the density in the infrared region of the thus obtained silverimages or silver sulfide images is utilized for the reproduction ofsound. The infrared density (transmitting density) of these silver orsilver sulfide images ranges generally from 1.0 to 0.6.

The production of sound tracks on a color print film can be carried outby using the procedures as described in, for example, Journal of theSociety of Motion Picture and Television Engineers, vol. 77, page 1154(1968).

According to these procedures, color images in picture areas and soundimages in sound track areas are color-developed at the same time in acolor developing bath. In a first fixing bath, unexposed silver halideis removed and, in a bleaching bath, developed silver produced by thedeveloping step is rehalogenated. In the sound developing step, silverhalide only in the sound track areas is converted to a silver image byselectively applying a viscous sound developer solution to the soundtrack areas. In a second fixing bath, the silver halide in the pictureareas is fixed and removed and, in a stabilizing bath, the image dyesare stabilized. The density in the infrared region of the silver imagesthus formed on a sound track is predominantly utilized for thereproduction of sound.

Therefore, in the production of sound tracks in a color film, the stepfor forming the silver images or the silver sulfide images isindispensable as described above. The reason for forming a sound trackcomprising silver or silver sulfide is, as described above, because thephotoelectric tube which is employed in the process of soundreproduction has its maximum sensitivity in the infrared region, whilein such region of the spectrum the density of color dyes formed by colordeveloping step is insufficiently low. Accordingly, the step to producesilver images or silver sulfide images in the sound track area is neededin addition to the step of forming dye images in the picture area.

Recently, methods to produce sound tracks without such a step have beenprovided. For example, as described in U.S. Pat. applications Ser. Nos.439,675, filed Feb. 4, 1974, 451,658, filed Mar. 15, 1974 and U.S. Pat.Nos. 3,705,801, 3,715,208, and 3,737,312, a color photographiclight-sensitive material which comprises an auxiliary layer containing acompound which is capable of protecting the sound image from the effectof a bleaching agent and restraining silver bleaching (a silver bleachinhibitor) is provided. When using a light-sensitive material asdescribed, it is possible to form sound images simply by conventionalcolor processing without conducting the so-called sound development.However, these light-sensitive materials having such an auxiliary layercontaining a silver bleach inhibitor entail certain disadvantages. Thatis, due to the formation of the auxiliary layer (the sound track forminglayer) in addition to the conventional image forming layers, thesensitivity of the image forming layers which are positioned under thesound track forming layer is reduced and the sharpness of the imagesdecreases markedly. For example, when the sound track forming layer isformed in the farthest position from the support (uppermost position),the frequency modulation property of the sound images is improved butthe sharpness of picture images decreases. On the contrary, when thesound track forming layer is located closest to the support, thesharpness of the picture images formed in the image forming layers overthe sound track forming layer is not affected but good frequencymodulation properties cannot be obtained. This is a great difficulty inthe practical use of these color photographic light-sensitive materialshaving such an auxiliary sound track forming layer.

Another method of forming sound tracks without a sound developing stepis described in Japanese Pat. application Laid Open No. 24431/74 andU.S. Pat. No. 3,705,800, in which a multilayer color photographiclight-sensitive material is developed to form a picture recordcomprising silver and a dye and a sound track record comprising silverand then a silver bleach inhibitor is selectively applied to the silverof the sound track record. in Japanese Pat. application Laid Open No.24431/74, the disclosure is that a compound having at least twooxyalkylene groups or a compound having at least one mercapto group canbe suitably used as the silver bleach inhibitor. According to the methoddescribed in Japanese Pat. application Laid Open No. 24431/74, afterdevelopment of a multilayer color photographic light-sensitive material,the silver bleach inhibitor as mentioned above is applied to only thesound track area containing silver to protect the silver sound trackrecord from the action of the silver bleaching agent, and then thematerial is treated in a single bleach-fixing bath. Although ashortening of the overall processing time can be achieved by treating insuch a bleach-fixing bath, this method is accompanied by the followingdisadvantage. That is, in order to recover silver from a treating bathfor a color photographic light-sensitive material, in particular amotion picture film, a method of electrolyzing the fixing solution isgenerally and preferably used. The method is described, for example, inJournal of the Society of Motion Picture and Television Engineers, vol.81, pages 603-608. However, when such a single bleach-fixing bath asdescribed in Japanese Patent Application Laid Open No. 24431/74, GermanPat. Nos. 866,605 and 966,410, and British Journal of Photography, pages122-123 and 126 (1966) is employed, the silver recovery by electrolysisis difficult to perform due to the presence of other metal ions than asilver ion such as an iron ion in the solution.

Also Japanese Pat. application Laid Open No. 13483/72 describes a methodfor preparing a sound track which comprises developing a multi-layercolor photographic light-sensitive material, contacting the sound trackarea containing silver with a silver bleach inhibitor having a mercaptogroup or a seleno group, and carrying out the bleaching step. Accordingto the method, the silver bleach inhibiting action may be enhanced byusing an onium salt such as a quaternary ammonium compound, a quaternaryphosphonium compound or a tertiary sulfonium compound together with thesilver bleach inhibitor having a mercapto group or a seleno group,however, the description is that these onium salts are not silver bleachinhibitors within the meaning of the term as defined therein.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a newmethod of forming an optical sound track.

Another object of the present invention is to provide a method offorming a sound record suitable for a color photographic light-sensitivematerial which is not subjected to a reversal processing step, such as,for example, a color print film (color positive film).

Still another object of the present invention is to provide a method offorming a sound record which can be easily composed into a series ofprocessing steps of a color photographic light-sensitive material.

A further object of the present invention is to provide a method offorming an excellent color image and sound record in a simple and rapidmanner using a conventional color photographic light-sensitive material.

These objects can be attained by applying a nitrogen containingheterocyclic compound in which at least one of the nitrogen atoms isconnected to a group having 6 or more carbon atoms to form a quaternarysalt ot a sound track area of a color-developed multi-layer colorphotographic light-sensitive material and then bleaching thecolor-developed material.

DETAILED DESCRIPTION OF THE INVENTION

The process of forming an optical sound track according to the presentinvention comprises contacting the sound track area of a colorphotographic material with a nitrogen containing heterocyclic compoundin which at least one of the nitrogen atoms is connected to a grouphaving 6 or more carbons atoms to form a quaternary salt to selectivelyrestrain the bleaching of silver in the sound track area, as a silverbleach inhibitor, after the color-developing but prior to the bleachingof the color photographic material.

The fact that the heterocyclic quaternary salt compound alone can beused effectively as a silver bleach inhibitor according to the presentinvention is very surprising when the description in the above-describedJapanese Pat. application Laid Open No. 13483/72 that the onium saltsare not silver bleach inhibitors is considered. Further, when the silverbleach inhibitor having a mercapto group or a seleno group and the oniumsalt are used in combination, it is occasionally found that the bleachinhibitor does not dissolve. However, such a disadvantage does not occurin the present invention in which the quaternary salt of the presentinvention is employed.

In a preferred embodiment of the present invention, the multi-layercolor photographic light-sensitive material comprises a support havingcoated thereon a first silver halide emulsion layer sensitive to a firstregion of the visible spectrum and containing a coupler capable offorming a yellow dye by reacting with an oxidation product of a colordeveloping agent, a second silver halide emulsion layer sensitive to asecond region of the visible spectrum and containing a coupler capableof forming a magenta dye by reacting with an oxidation product of acolor developing agent, and a third silver halide emulsion layersensitive to a third region of the visible spectrum and containing acoupler capable of forming a cyan dye by reacting with an oxidationproduct of a color developing agent. The light-sensitive material canfurther include a backing layer containing carbon black, etc., a subbinglayer, an antihalation layer containing black colloidal silver, etc., ayellow filter layer containing yellow colloidal silver, etc., a gelatininter layer, a protective layer, and the like.

An image exposure from a picture original and a sound image exposurefrom a sound original are provided to a multilayer color photographiclight-sensitive material, for example such as those described above, andthe photographic material is subjected to color development to formimages comprising a silver image and dye image in the picture recordarea and the sound record area. A solution containing a silver bleachinhibitor is then applied to only the sound track area of thephotographic material. Upon bleaching the photographic material thesilver image in the picture area is bleached, whereas the silver imagein the sound track area remains which is treated with the silver bleachinhibitor to render the silver unbleachable. Subsequently thephotographic material is treated with a fixing solution to remove theunexposed silver halide and the bleached silver while the silver imagein the sound track area remains. Thus the dye image in the picture areaand the silver image in the sound track area are formed. The silverimage in the sound track area can be utilized as a sound image.

In another preferred embodiment of the present invention, a photographicmaterial can be treated with a pre-bath in order to remove a backinglayer prior to color development, or can be treated with a pre-hardeningbath for hardening the photographic layers prior to color development.

In a further preferred embodioment of the present invention, aphotographic material can be treated, after color development but priorto applying a silver bleach inhibitor to the sound track area, with astop bath, a stop-fixing bath or a fixing bath.

In a still further preferred embodiment of the present invention, aphotographic material can be treated with a stabilizing bath tostabilize the color images after the fixing treatment. Further betweeneach treatment step a washing step can be interposed.

The term "sound track area" or "sound record area" as used in thisspecification refer to the area of a motion picture film as the areaseen in a plane view, and the position and the width are defined asdescribed in ASTM PH 22.40-1967 for 35 mm film and ASTM PH 22.41-1969for 16 mm film.

The silver bleach inhibitor employed in the present invention is anitrogen containing heterocyclic compound in which at least one of thenitrogen atoms is connected to a group having 6 or more carbon atoms upto about 100 carbon atoms to form a quaternary salt. The number ofcarbon atoms which is contained in the group connected to the nitrogenatom greatly influences the silver bleach inhibiting action of thecompound. A nitrogen containing heterocyclic compound in which a grouphaving 4 carbon atoms connected to the nitrogen atom to form aquaternary salt does not exhibit any silver bleach inhibiting action.Compounds having a group of 8 or more carbon atoms connected to thenitrogen atom show a particularly preferred silver bleaching action.Compounds in which the nitrogen containing heterocyclic ring is selectedfrom a pyridine ring, an imidazole ring or a quinoline ring areparticularly advantageous.

The nitrogen containing heterocyclic ring can have substituents on thering forming atoms other than the quaternary nitrogen atom. Of thesesubstituents an alkyl group having 1 to 12 carbon atoms, for example, amethyl group, an ethyl group, a propyl group, a butyl group, a hexylgroup, an octyl group, a dodecyl group, etc., is preferred. The groupsconnected to the nitrogen atom having 6 or more carbon atoms include asubstituted or unsubstituted alkyl or alkenyl group. Suitable alkylgroup substituents include a hydroxy group, an alkoxy group, an aryloxygroup, an acyloxy group, an acylamino group, an amino group, a carbamoylgroup, an alkylthio group, an aryl group and the like. In the compoundwhich can be used in the present invention, the anion which forms thequaternary salt is not limited and those derived from a bromide, achloride, a thiocyanate, a sulfonate, a perchlorate, etc., can bepreferably used.

Compounds which can be advantageously used as silver bleach inhibitorsin the present invention are a pyridinum salt, an imidazolium salt and aquinolium salt. The compounds represented by the following generalformula (I) are particularly preferred.

General Formula (I) ##EQU1## wherein Z represents the atoms necessary toform a substituted or unsubstituted pyridine ring, imidazole ring orquinoline ring; X⁻ represents an anion; and R₁ represents a group having6 or more carbon atoms and selected from the following groups (a) to(d):

a. a substituted or unsubstituted alkyl or alkenyl group, ##EQU2##wherein R₂ represents a substituted or unsubstituted alkyl or alkenylgroup or alkaryl group; R₃ represents a hydrogen atom or a methyl group;A represents --O--, --S--, --COO-- or --NCH₃ --; B represents --O--,--COO--, --CONH-- or --CONHC₂ H₄ CONH-; C represents an oxyalkylenegroup; D represents -- CH₂ CH₂ -- or --O--; m represents an integer of 1to 40; n represents 0 or 1; and p represents 0 or 1. The alkyl oralkenyl moiety in (a) above preferably has 6 to 30 carbon atoms andpreferred substituents are a hydroxy group, a halogen atom, and an arylgroup, etc. Examples of unsubstituted alkyl groups include, for example,a hexyl group, an octyl group, a decyl group, a dodecyl group, atetradecyl group, an octadecyl group, a nonadecyl group, and the like.Examples of substituted alkyl groups include, for example, a1,1-2H-perfluorooctyl group, a p-nonylbenzyl group, a p-octylbenzylgroup, a p-tert-butylbenzyl group, and the like. Suitably R₂ in (b), (c)and (d) above can have from 3 to 20 carbon atoms in the alkyl moietythereof and examples of substituents include a hydroxy group, a halogenatom, an aryl group, etc. Examples of unsubstituted alkyl groups includean octyl group, a dodecyl group, a 2-methyldodecyl group, a 2-ethylhexylgroup, etc., and examples of substituted alkyl groups include a1,1-2H-perfluorooctyl group, a p-nonylbenzyl group, ap-tert-butyl-benzyl group, etc. Suitable examples of oxyalklylene groupsinclude an oxyethylene group and an oxypropylene group. Specificexamples of silver bleach inhibitors which can be used in the presentinvention are illustrated below. ##EQU3##

The silver bleach inhibitors used in the present invention can be easilyprepared using conventional methods. For example, the methods describedin Kogyo Kagaku Zasshi (Journal of Industrial Chemistry), vol. 63, pages595-600 (1960) or in U.S. Pat. No. 3,545,974 can be utilized. A specificexample of the synthesis is illustrated below as to Compound 9.

1284 g of tetradecyl alcohol was dissolved by heating and 2.0 g ofstannic tetrachloride was added as a catalyst. With vigorous stirring148 g of epichlorohydrin was added at once. After a reaction time of 3hours at 120°-130°C with stirring, the reaction mixture was cooled to45°-50°C and a small amount of an aqueous solution of potassiumcarbonate was added and the mixture was vigorously stirred to decomposethe catalyst. The mixture was dried by addition of anhydrous sodiumsulfate, then filtered and distilled under reduced pressure to separateunreacted tetradecyl alcohol from the crude product. The crude productwas again distilled to give 350 g oftetra-decyl-3-chloro-2-hydroxypropyl ether with a boiling point of176°-180°C/3 mmHg (yield 73.3 percent). 307 g oftetradecyl-3-chloro-2-hydroxypropyl ether and 237 g of pyridine wereadded to a flask and refluxed for 10 hours at 130°-140°C. After cooling,excess pyridine was removed by distillation under reduced pressure. Theresidue was recrystallized from a solvent mixture of acetone andethanol. 272 g of 2-hydroxy-3-tetradecyloxypropyl pyridinium chloridewith a melting point of 91°C was obtained (yield 71.5%). Other compoundscan be prepared in a similar manner according to the method above.

The silver bleach inhibitor in the present invention can be used aloneor as a combination of two or more thereof. When a combination of two ormore is used, it is observed that the silver bleach inhibiting functionis occasionaly increased to an even greater extent. Also the silverbleach inhibitor of the present invention can be used together withother compounds which have a silver bleach inhibiting function or whichpromote the silver bleach inhibiting function. Suitable examples ofthese compounds are described in U.S. Pat. application Ser. No. 360,507,filed May 15, 1973, now U.S. Pat. No. 3,869,287 and aforementioned U.S.Pat. application Ser. No. 451,658, filed Mar. 15. 1974.

In accordance with the present invention, it is only necessary to beinga solution containing the silver bleach inhibitor into contact with asound track area of a photographic material after color development butprior to a bleaching step. The contacting procedure is not dependentupon critical concentrations, times or temperature. The silver bleachinhibitor is generally applied as an aqueous solution. The solution,however, can contain an organic solvent which is miscible with water,for example, such as methanol, ethanol, etc.

The solution containing a silver bleach inhibitor which can be used inthe present invention can contain a conventional thickening agent suchas a tragacanth gum, a xanthane gum, a copolymer of methyl vinyl etherand maleic anhydride (available from GAF Corporation under the tradename of Gantrez-AN-4651) to increase the viscosity.

The concentration of the silver bleach inhibitor in the silver bleachinhibitor treatment solution used in the present invention can rangegenerally from about 0.5 to about 30 weight%. and preferably from 1 to20 weight%. The treatment solution containing the silver bleachinhibitor can be applied to a color photographic material over any rangeof acidic, neutral and alkaline. A preferred range is from a pH of about5 to a pH of about 13.

The temperature at which the silver bleach inhibitor solution can bebrought into contact with the sound track area can vary widely. However,use of approximately the same temperature as the temperature employedfor the remainder of the processing solutions is preferred. Photographicprocessing temperatures conventionally range from about 20°C or less toabout 60°C or higher, preferably about 30°C to 55°C, and the procedureof the present invention can be preferably carried out in this range.

The time the silver bleach inhibitor solution can be in contact with asound track area can also vary widely. Usually the time ranges fromabout 5 seconds or less to about 10 minutes or more and preferably, itranges from about 20 seconds to about 5 minutes.

The silver bleach inhibitor solution can be applied to a colorphotographic material using any convenient method. A sound applicatorwhich has been used for coating a sound developer on a sound track areaof a color photographic material is particularly useful.

As the support for the photographic material used in the presentinvention to which light-sensitive silver halide emulsion layers areapplied, a cellulose ester film such as cellulose nitrate, celluloseacetate, etc., a polyester film such as polyethylene terephthalate,etc., a polyvinyl chloride film, a polystyrene film, a polycarbonatefilm and the like are illustrated and are preferred.

Any known hydrophilic colloids used in silver halide emulsion layers canbe used. Gelatin, a gelatin derivative (for example an acylated gelatinsuch as described in U.S. Pat. No. 3,118,766, a graft gelatin having asa graft portion a vinyl monomer such as acrylic acid, etc., as describedin U.S. Pat. No. 2,831,767), albumin, gum arabic, agar-agar, a cellulosederivative (an alkyl ester of carboxymethyl cellulose, hydroxyethylcellulose, carboxymethyl hydroxyethyl cellulose, etc.), a syntheticresin (polyvinyl alcohol, polyvinyl pyrrolidone, etc.) and the like arepreferred. These hydrophilic colloids can also be used as the binder forlayers which constitute the light-sensitive material (for example, aprotective layer, a filter layer, an inter layer, an antihalation layer,a subbing layer, a backing layer, etc.) other than the emulsion layers.

The hydrophilic colloid used in the various layers of thelight-sensitive material is advantageously hardened with a hardener ofan aldehyde type, a methylol type, a 1,4-dioxane type, an aziridinetype, an ioxazole type, a carbodiimide type, an active halogen type, anactive vinyl type and the like.

Typical examples of these hardeners are described in U.S. Pat. Nos.3,232,764; 3,288,775; 2,732,303; 3,635,718; 3,232,763; 2,732,316;2,586,168; 3,103,437; 3,017,280; 2,983,611; 2,725,294; 2,725,295;3,100,704; 3,091,537; 3,543,292 and British Pat. Nos. 974,723; 1,167,207and 994,869, etc.

In the light-sensitive material in the present invention, all silverhalide emulsions which are used in the photographic field, for example,silver bromide, silver iodobromide, silver chloroiodobromide, silverchlorobromide, silver chloride, etc. emulsions can be used. Further theso-called converted-halide silver halide grains such as described inBritish Pat. No. 635,841 and U.S. Pat. No. 3,622,318, etc. are alsouseful.

The silver halide photographic emulsion of the light-sensitive materialused in the present invention can be chemically sensitized using thenatural sensitizers in gelatin. The emulsion can also be chemicallysensitized with a sulfur compound as described in U.S. Pat. Nos.1,547,944; 1,623,499 and 2,410,689. The emulsion can be chemicallysensitized with a palladium or a gold salt as described in U.S. Pat.Nos. 2,399,083 and 2,642,361. The emulsion can also be sensitized with areducing agent such as a stannous salt as described in U.S. Pat. No.2,487,850, or a reducing agent such as a polyamine as described in U.S.Pat. No. 2,521,925. The emulsion can further be spectrally sensitizedwith a cyanine dye or a merocyanine dye as described in U.S. Pat. Nos.2,519,001; 2,666,761; 2,734,900; 2,739,964 and 3,481,742. The emulsioncan contain a stabilizer such as a mercury compound, an azaindene, etc.,a plasticizer such as glycerin, etc., a coating aid such as saponin,polyethylene glycol monolauryl ether, etc. The emulsion can furthercontain an antistatic agent, a ultraviolet absorber, a fluorescentbrightening agent, a dye and the like.

In the present invention, all open-chain ketomethylene type yellow dyeforming color couplers can advantageously be used. Typical examplesthereof include a benzoylacetanilide type color coupler, a pivaloylacetanilide type color coupler, etc. All magenta dye forming colorcouplers such as a pyrazolone type, a indazolone type, etc., canadvantageously be used. Also, all cyan dye forming couplers such as aphenol type and a naphthol type, etc. can be advantageously used. Thesecolor couplers can have a coupling releasing group at the active carbonatom of the coupling position. Color couplers which are rendednon-diffusible by introducing a ballasting group in the molecule arepreferred. The terms "coupling releasing group," "ballasting group" and"non-diffusible" are conventionally used in connection with colorcouplers, and their meanings are well known to those skilled in the art.Various kinds of these color couplers are well known. Particularlypreferred color couplers are selected from a yellow dye forming colorcoupler capable of reacting with an oxidation product of a colordeveloping agent to form a dye having an absorption maximum in thewavelength region of about 420 to 460 mμ, a magenta dye forming colorcoupler to form a dye having an absorption maximum in the wavelengthregion of about 520 to 570 mμ and a cyan dye forming color coupler toform a dye having an absorption maximum in the wavelength region ofabout 630 to 710 mμ.

Specific examples of non-diffusible color couplers are described in, forexample, U.S. Pat. Nos. 1,108,028; 2,186,849; 2,206,142; 2,343,702;2,367,531; 2,369,489; 2,423,730; 2,436,130; 2,474,293; 2,600,788;2,689,793; 2,728,658; 2,742,832; 2,808,329; 2,998,314; 3,046,129;3,062,653; 3,265,506; 3,311,476; 3,408,194; 3,419,390; 3,419,391;3,458,315; 3,476,563; 3,516,831; 3,617,291 and British Pat. No.1,183,515, etc.

These color couplers can be incorporated into the hydrophillic colloidof the photographic material using any known technique. For example, thecolor couplers can be dissolved in a high boiling organic solvent (e.g.,boiling above 170°C) such as dibutyl phthalate, tricresyl phosphate,etc. as described in U.S. Pat. No. 2,322,027 and if desired togetherwith a low boiling organic solvent (e.g., boiling below 170°C) such asethyl acetate, tetrahydrofuran, etc., and the solution is dispersed inthe hydorphilic colloid. Also, where the color couplers contain an acidgroup such as a carboxylic acid group or a sulfonic acid group, they canbe incorporated into the hydrophilic colloid as an aqueous alkalinesolution.

In accordance with the present invention, a multi-layer colorphotographic light-sensitive material is exposed to form a picture imageand a sound image, subjected to color development to form a picturerecord and a sound record containing silver, brought into contact withthe silver bleach inhibitor only at the sound record area, and bleachedto remove the silver only from the picture record area while in thesound record area a greater part of the silver remains, and thus a colorphotographic material having a sound track comprising silver can beobtained.

With respect to the photographic processing steps, all processingsconventionally used in a processing of color photographic materials canbe utilized except for the procedure of applying the silver bleachinhibitor to the sound track area.

Useful color developer solutions are aqueous alkaline solutionscontaining a color developing agent. As the color developing agent, allknown primary aromatic amino dye forming developing agents, for examplea para-phenylenediamine (for example, N,N-diethyl-para-phenylenediamine,N-ethyl-N-hydroxyethyl-para-phenylenediamine,N-ethyl-N-hydroxyethyl-2-methylpara-phenylenediamine,N-ethyl-N-β-methanesulfonamidoethyl3-methyl-4-aminoaniline,N,N-di-ethyl-2-methyl-para-phenylenediamine, and the sulfates,hydrochlorides or sulfites thereof, etc.) can be used and are preferred.These are well known in the art, for example, as described in C. E. K.Mees and T. H. James The Theory of the Photographic Process, page294-295, The Macmillan Co., 1966; U.S. Pat. Nos. 2,592,364 and2,193,015, etc. The color developer solution can further containadditives conventionally used for example, a sulfite, a carbonate, abisulfite, a bromide, or an iodide of an alkali metal, benzyl alcoholand the like.

All bleaching solutions containing known bleaching agents such as aferricyanide, a bichromate, an iron (III) salt, etc. can be used. Anysilver oxidizing agent used in a conventional bleaching solution can beused in the bleaching bath in the present invention. For example, awater-soluble ferricyanide (e.g., sodium ferricyanide, potassiumferricyanide, ammonium ferricyanide, etc.), a water-soluble quinone(e.g., quinone, chloroquinone, methylquinone, etc.), a water-solubleferric salt (e.g.) ferric chloride, ferric sulfate, ferric thiocyanate,ferric oxalate, etc.), a water-soluble cupric salt (e.g., cupricchloride, cupric sulfate, etc.), a water-soluble cobaltic salt (e.g.,cobaltic chloride, ammonium cobaltic nitrate, etc.) and the like can beused. Further, a complex salt between a polyvalent cation and an alkalimetal and a water-soluble organic acid can also preferably be used.Suitable organic acids include compounds represented by the followingformula.

    HOOC - Q.sub.1 -- X -- Q.sub.2 -- COOH

or ##EQU4## wherein X represents a hydrocarbon group, an oxygen atom, asulfur atom or a -NQ₆ group, Q₁, Q₂, Q₃, Q₄ and Q₅ each represents asubstituted or unsubstituted hydrocarbon group, and Q₆ represents ahydrogen atom or a substituted or unsubstituted hydrocarbon group.

Typical examples of suitable organic acids are malonic acid, tartaricacid, ethylmalonic acid, malic acid, fumaric acid, diglycoloic acid,thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid,ethylenediamine tetraacetic acid, aminotriacetic acid,ethylenedithioglycollic acid, dithioglycollic acid, dithioglycollic acidand the like.

Examples of polyvalent cations include a ferric ion, a cobaltic ion anda cupric ion. An iron sodium complex salt of ethylenediaminetetraaceticacid is particularly useful as a bleaching agent.

Specific examples of bleaching solutions are described in, for example,Journal of the Society of Motion Picture and Television Engineers, vol.61, pages 667-701 (1953); U.S. Pat. No. 3,189,452; German Pat. Nos.866,605 and 966,410; U.S. Pat. No. 3,582,322; and British Journal ofPhotography, vol. 107, pages 122-123 and 126 (1966).

For removing the soluble silver salt from a photographic material afixing solution is used. All fixing solutions containing a compoundconventionally used as a solvent for silver halide can be used. Forexample a water-soluble thiosulfate (e.g., sodium thiosulfate, potassiumthiosulfate, ammonium thiosulfate etc.), a water-soluble thiocyanate(e.g., sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate,etc.), a water-soluble organic diol fixing agent containing an oxygenatom or a sulfur atom (e.g., 3-thia-1,5-pentanediol,3,6-dithia1,8-octanediol,9-oxa-3,6,12,15-tetrathia-1,17-heptadecanediol, etc.), a water solublesulfur-containing organic dibasic acid and a water-soluble salt thereof(e.g., ethylene bisthioglycollic acid, sodium salt thereof, etc.), aimidazolidinethione (e.g., methylimidazolidinethione, etc.) and the likeare preferably used.

Further, the fixing agents described in L. F. A. Mason, PhotographicProcessing Chemistry, pages 187-188, Focal press (1966) can alsopreferably be used.

The bleaching step and the fixing step can be carried out in a singlebath, if desired. In such case, the above described bleaching agent andfixing agent can be used in a suitable combination. Specific examples ofthe bleach-fixing baths are described in, for example, German Pat. No.866,605 and U.S. Pat. No. 3,582,322, etc.

Each processing bath can advantageously be used in a system in which thebaths are circulated for regeneration. Such a process is described in,for example, Journal of the Society of Motion Picture and TelevisionEngineers, vol. 81, pages 293-295 (1972), etc.

Silver can be advantageously recovered from the fixing solution. Amethod of silver recovery is described in, for example, Journal of theSociety of Motion Picture and Television Engineers, vol. 81, pages603-608, etc.

The invention will now be explained in greater detail by reference tothe following examples. Unless otherwise indicated, all parts, percents,ratios and the like are by weight.

EXAMPLE 1

On a surface of cellulose triacetate film support which has ananti-halation layer containing carbon black on the other surface, asubbing layer was provided, on which a coating solution containing asilver iodobromide emulsion containing 1.2 mol % of iodide (containing0.05 mol of silver) and a dispersion prepared by dispersingα-(2-methylbenzoyl)-3-[α-(2,4-di-tert-amylphenyoxy)-acetamido]acetanilide, as a yellow coupler, together with dibutyl phthalate andethyl acetate was applied to form a blue-sensitive layer. On theblue-sensitive layer, a gelatin inter layer was applied. On the interlayer a coating solution containing a silver chlorobromide emulsioncontaining 30 mol% of the bromide (containing 0.06 mol of silver) whichwas spectrally sensitized so as to have a sensitivity maximum at about685 mμ and a dispersion prepared by dispersing1-hydroxy-4-chloro-2-(N-hexadecyl)-naphthamide, as a cyan coupler,together with dibutyl phthalate was applied to form a red-sensitivelayer. The optical sensitizing dye used has the following structure:##SPC1##

On the red-sensitive layer, a gelatin inter layer was applied. On theinter layer a coating solution containing a silver chlorobromideemulsion containing 35 mol% of the bromide (containing 0.06 mol ofsilver) which was spectrally sensitized so as to have a sensitivitymaximum at about 555 mμ and a dispersion prepared by dispersing1-(2,6-dichloro-4-methylphenyl)-3-{3-[α-(2,4-di-tert-amylphenoxy)butyramido]benzamido}-5-pyrazoloneand1-(2,4,6-trichlorophenyl)-3-[3-{α-(2,4-di-tert-amylphenoxy)-butyramido}benzamido]-5-pyrazolone,as a magenta coupler, together with tricresyl phosphate and ethylacetate was applied to form a green-sensitive layer. The opticalsensitizing dye had the following structure: ##SPC2##

Subsequently, a coating solution containing liquid paraffin dispersed inan aqueous gelatin solution was coated to form a protective layer. Thus,a color print film which was designated Sample (I) was prepared.

In Sample (I), the coating amount of silver, coupler and gelatin(binder) and the thickness of a coating layer were as follows.

    Layer        Silver   Coupler  Gelatin                                                                              Thickness                               ______________________________________                                        Blue-sensitive Layer                                                                       1.2 g/m.sup.2                                                                          1.2 g/m.sup.2                                                                          2.7 g/m.sup.2                                                                        4.3 μ                                Inter Layer  --       --       0.8 g/m.sup.2                                                                        0.6 μ                                Red-sensitive Layer                                                                        0.8 g/m.sup.2                                                                          1.2 g/m.sup.2                                                                          1.7 g/m.sup.2                                                                        3.1 μ                                Inter Layer  --       --       0.8 g/m.sup.2                                                                        0.6 μ                                Green-sensitive Layer                                                                      1.1 g/m.sup.2                                                                          1.2 g/m.sup.2                                                                          3.0 g/m.sup.2                                                                        4.2 μ                                Protective Layer                                                                           --       --       0.8 g/m.sup.2                                                                        0.6 μ                                ______________________________________                                    

The amount of sensitizing dye to silver was as follows:

    Red-sensitive Layer                                                                              25  mg/mole of silver                                      Green-sensitive Layer                                                                            250 mg/mole of silver                                  

Sample (I) was stepwise exposed to radiation from a light source of atungsten lump through a silver wedge and subjected to processingaccording to Processing A, Processing B or Processing C. The infrareddensity of each film thus treated was measured with a Macbeth TD-206Atype densitometer using a Status S-58 filter. The results obtained areshown in Table 1.

    ______________________________________                                        Processing A                                                                  Processing Step                                                                              Temperature   Time                                             ______________________________________                                        Pre-bath       27°C   10 sec.                                          Washing        "             15 sec.                                          Color Development                                                                            "             5 min. 20 sec.                                   Washing        "             15 sec.                                          First Fixing   "             1 min.                                           Washing        "             40 sec.                                          Bleaching      "             3 min.                                           Washing        "             1 min.                                           Sound Development                                                                            Room Temperature                                                                            15 sec.                                          Washing        27°C   15 sec.                                          Second Fixing  "             2 min.                                           Washing        "             5 min.                                           Stabilizing    "             10 sec.                                          ______________________________________                                    

The compositions of the processing solutions used were as follows.

    ______________________________________                                        Pre-bath Solution                                                             Water                   800      ml                                           Sodium Carbonate (monohydrate)                                                                        10.0     g                                            Sodium Sulfate (anhydrous)                                                                            50.0     g                                            Water to make           1.0      liter                                        Color Developer Solution                                                      Water                   800      ml                                           Sodium Hexametaphosphate                                                                              2.0      g                                            Sodium Sulfite (anhydrous)                                                                            4.0      g                                            2-Amino-5-diethylaminotoluene                                                                         3.0      g                                            Hydrochloride                                                                 Sodium Carbonate (monohydrate)                                                                        25.0     g                                            Potassium Bromide       2.0      g                                            Water to make           1.0      liter                                        First Fixing Solution and Second Fixing                                       Solution                                                                      Water                   600      ml                                           Sodium Thiosulfate (pentahydrate)                                                                     240      g                                            Sodium Sulfite (anhydrous)                                                                            15.0     g                                            Glacial Acetic Acid     12.0     g                                            Boric Acid              6.0      g                                            Potassium Alum          15.0     g                                            Water to make           1.0      liter                                        Bleaching Solution                                                            Water                   800      ml                                           Potassium Bromide       20.0     g                                            Potassium Bichromate    5.0      g                                            Potassium Alum          40.0     g                                            Sodium Acetate (trihydrate)                                                                           3.0      g                                            Glacial Acetic Acid     10.0     g                                            Water to make           1.0      liter                                        Sound Developer Solution                                                      Solution A                                                                    Water                   600      ml                                           Sodium Sulfite (anhydrous)                                                                            40.0     g                                            N-Methyl-p-aminophenol Sulfate                                                                        40.0     g                                            Sodium Hydroxide        40.0     g                                            Hydroquinone            40.0     g                                            Solution B                                                                    Water                   300      ml                                           Tragacanth Gum          5.0      g                                            Denatured Alcohol       10       ml                                           Solution C                                                                    Ethylenediamine (70%)   20       ml                                           Solution A and Solution B were mixed                                          together and immediately before use,                                          Solution C and water were added                                               thereto to make 1.0 liter.                                                    Stabilizing Solution                                                          Water                   800      ml                                           Formaldehyde (37%)      10       ml                                           40% Aqueous Solution of Poly-                                                                         5        ml                                           ethylene glycol                                                               molecular weight: 400)                                                        Water to make           1.0      liter                                        ______________________________________                                    

    Processing B                                                                  ______________________________________                                        Processing Step                                                                              Temperature Time                                               ______________________________________                                        Pre-bath       27°C 10 sec.                                            Washing        "           15 sec.                                            Color Development                                                                            "           5 min. 20 sec.                                     Washing        "           15 sec.                                            First Fixing   "           1 min.                                             Washing        "           40 sec.                                            Bleaching      "           3 min.                                             Washing        "           1 min.                                             Second Fixing  "           2 min.                                             Washing        "           5 min.                                             Stabilizing    "           10 sec.                                            ______________________________________                                    

The compositions of the processing solutions were the same as describedin Processing A.

    ______________________________________                                        Processing C                                                                  ______________________________________                                        Processing Step  Temperature                                                                              Time                                              ______________________________________                                        Pre-bath         27°C                                                                              10 sec.                                           Washing          "          15 sec.                                           Color Development                                                                              "          5 min. 20 sec.                                    Washing          "          15 sec.                                           First Fixing     "          1 min.                                            Washing          "          40 sec.                                           Silver Bleach Inhibiting                                                                       Room       30 sec.                                                            Temperature                                                  Washing          27°C                                                                              1 min.                                            Bleaching        "          3 min.                                            Washing          "          1 min.                                            Second Fixing    "          2 min.                                            Washing          "          5 min.                                            Stabilizing      "          10 sec.                                           ______________________________________                                    

The compositions of the Silver Bleach Inhibitor Solution and theBleaching Solution were as follows.

    ______________________________________                                        Silver Bleach Inhibitor Solution                                              Water                    800     ml                                           Silver Bleach Inhibitor of the                                                                         100     g                                            Present Invention (Compound 4)                                                Water to make            1.0     liter                                        Bleaching Solution                                                            Water                    700     ml                                           Ammonium Bromide         150     g                                            Tetrasodium Iron (III) Salt of                                                                         130     g                                            Ethylenediamine Tetraacetic Acid                                              Sodium Acetate           15      g                                            Water to make            1.0     liter                                        ______________________________________                                    

The compositions of the processing solutions other than the SilverBleach Inhibitor Solution and the Bleaching Solution were the same asdescribed in Processing A.

                  Table 1                                                         ______________________________________                                                     Processing                                                                    A       B         C                                              ______________________________________                                        Infrared Density                                                                             1.90      0.35      1.70                                       ______________________________________                                    

From the results shown in Table 1, it will be understood that byapplying the silver bleach inhibitor according to the present inventiona high infrared density nearly comparable to that obtained by aconventional process including a sound development step can be obtained,while a very low infrared density was obtained when using Processing B.

EXAMPLE 2

Sample (I) as described in Example 1 was exposed using the sameprocedure as described in Example 1 and subjected to processingaccording to Processing D or Processing E. The infrared densities of thesamples were measured in the same manner as described in Example 1. Theresults obtained are shown in Table 2.

    ______________________________________                                        Processing D                                                                  ______________________________________                                        Processing Step  Temperature                                                                              Time                                              ______________________________________                                        Pre-bath         37.8°C                                                                            15 sec.                                           Washing          "          30 sec.                                           Color Development                                                                              "          2 min. 30 sec.                                    Stop             "          30 sec.                                           Washing          "          30 sec.                                           Silver Bleach Inhibiting                                                                       Room       30 sec.                                                            Temperature                                                  Washing          37.8°C                                                                            1 min.                                            Bleaching        "          1 min. 20 sec.                                    Washing          "          1 min.                                            Fixing           "          2 min.                                            Washing          "          2 min.                                            Stabilizing      "          10 sec.                                           ______________________________________                                    

The compositions of the processing solutions were as follows.

    ______________________________________                                        Pre-bath Solution                                                             The same as the Pre-bath Solution of Processing A                             Color Developer Solution                                                      Water                     900    ml                                           Trisodium Salt of Nitrilotriacetic                                                                      1      g                                            Acid                                                                          Sodium Sulfite            4      g                                            Sodium Carbonate (monohydrate)                                                                          30     g                                            Potassium Bromide         2      g                                            Hydroxylamine Sulfate     2      g                                            4-Amino-3-methyl-N-ethyl-N-β-                                            hydroxyethylaniline       4      g                                            Water to make             1.0    liter                                        Stop Solution                                                                 Water                     800    ml                                           Glacial Acetic Acid       30     ml                                           Water to make             1.0    liter                                        Silver Bleach Inhibitor Solution                                              Water                     800    ml                                           Silver Bleach Inhibitor of the                                                                          20     g                                            Present Invention (Compound 9)                                                10% Aqueous Solution of Sodium                                                                          10     ml                                           Hydroxide                                                                     Water to make             1.0    liter                                        Bleaching Solution                                                            The same as the Bleaching Solution of Processing C.                           Fixing Solution                                                               Water                     700    ml                                           Sodium Tetrapolyphosphoric Acid Salt                                                                    2      g                                            Sodium Sulfite            5      g                                            Sodium Thiosulfate (70%)  120    ml                                           Sodium Bisulfite          5      g                                            Water to make             1.0    liter                                        ______________________________________                                    

STABILIZING SOLUTION

The same as the Stabilizing Solution of Processing A.

PROCESSING E

The same as Processing D except for omitting the Silver BleachInhibiting Step.

                  Table 2                                                         ______________________________________                                        Processing        Infrared Density                                            ______________________________________                                        Processing D      1.40                                                        Processing E      0.35                                                        ______________________________________                                    

By Processing D according to the present invention a high infrareddensity was obtained, whereas in Processing E in which the Silver BleachInhibitor Solution was not used only a low infrared density wasobtained.

EXAMPLE 3

Sample (I) as described in Example 1 was exposed using the sameprocedure as described in Example 1 and subjected to processingaccording to Processing F which is the same as Processing D described inExample 2 except for the Silver Bleach Inhibitor Solution. Thecompositions of the Silver Bleach Inhibitor Solutions used in ProcessingF are shown in Table 3. After processing, the infrared densities of thesamples were measured in the same manner as described in Example 1. Theresults are shown in Table 4.

                                      Table 3                                     __________________________________________________________________________    Silver Bleach                                                                          F-1    F-2    F-3    F-4                                             Inhibitor                                                                     Solution                                                                      __________________________________________________________________________    Water    800 ml 800 ml 800 ml 800 ml                                          Silver Bleach                                                                 Inhibitor of                                                                           Compound 9                                                                           Compound 2                                                                           Compound 9                                                                           Compound 4                                      the Present                                                                            20 g   100 g  20 g   100 g                                           Invention                                                                              --     --     Compound 2                                                                           Compound 2                                                             100 g  100 g                                           10% NaOH Aq.                                                                           10 ml  --     10 ml  --                                              Solution                                                                      Water to 1 liter                                                                              1 liter                                                                              1 liter                                                                              1 liter                                         make                                                                          __________________________________________________________________________

                  Table 4                                                         ______________________________________                                        Silver Bleach Inhibitor Solution                                                                   F-1    F-2    F-3  F-4                                   ______________________________________                                        Infrared Density     1.40   1.25   2.35 2.14                                  ______________________________________                                    

It will be apparent that a high infrared density can be obtained usingthe silver bleach inhibitor according to the present invention, and thatthe effect can be increased by using two or more silver bleachinhibitors in combination.

EXAMPLE 4

Sample (I) as described in Example 1 was exposed using the sameprocedure as described in Example 1 and subjected to processingaccording to Processing G which is the same as Processing D described inExample 2 except for using the following solutions as the Silver BleachInhibitor Solution and the Bleaching Solution.

After processing, the infrared density of the sample was measured in thesame manner as described in Example 1 and it was 1.85. In this example ahigh infrared density was also obtained.

    ______________________________________                                        Silver Bleach Inhibitor Solution                                              Water                   800     ml                                            Silver Bleach Inhibitor of the                                                                        20      g                                             Present Invention (Compound 9)                                                Silver Bleach Inhibitor of the                                                                        100     g                                             Present Invention (Compound 2)                                                10% Aqueous Sodium Hydroxide                                                                          10      ml                                            Solution                                                                      Water to make           1.0     liter                                         Bleaching Solution                                                            Water                   800     ml                                            Ferric Chloride         30      g                                             Citric Acid             10      g                                             Water to make           1.0     liter                                         ______________________________________                                    

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A process for forming an optical sound trackwhich consists essentially of applying a nitrogen containingheterocyclic compound in which at least one of the nitrogen atoms isconnected to a group having 6 or more carbon atoms to form a quaternarysalt to a sound track area of a multi-layer color photographic material,after color developing but prior to bleaching wherein said nitrogencontaining heterocyclic compound is represented by the general formula:##EQU5## wherein Z represents the atoms necessary to form a pyridinering, an imidazole ring or a quinoline ring; X⁻ represent an anion; R₁represents a group having 6 or more carbon atoms and is selected fromthe group consisting ofa. an alkyl or an alkenyl group, ##EQU6## whereinR₂ represents an alkyl group, an alkenyl group, or an alkylaryl group;R₃ represents a hydrogen atom or a methyl group; A represents --O--,--S--, --COO--, or --NCH₃ --; B represents --O--, --COO--, --CONH--, or--CONHC₂ H₄ CONH--; C represents an oxyalkylene group; D represents--CH₂ CH₂ -- or --O--; m represents an integer of 1 to 40; n representsO or 1; and p represents O or
 1. 2. A process for forming an opticalsound track which consists essentially of applying a nitrogen containingheterocyclic compound in which at least one of the nitrogen atoms isconnected to a group having 6 or more carbon atoms to form a quaternarysalt to a sound track area having a silver image of a multi-layer colorphotographic material, after color developing but prior to bleachingwherein said nitrogen containing heterocyclic compound is represented bythe general formula; ##EQU7## wherein Z represents the atoms necessaryto form a pyridine ring, an imidazole ring or quinoline ring; X⁻represent an anion; and R₁ represents a group having 6 or more carbonatoms and is selected from the group consisting ofa. an alkyl or analkenyl group, ##EQU8## wherein R₂ represents an alkyl group, an alkenylgroup, or an alkylarly group; R₃ represents a hydrogen atom or a methylgroup; A represents --O--, --S--, --COO--, or --NCH₃ --; B represents--O--, --COO--, --CONH--, or --CONHC₂ H₄ CONH--; C represents anoxyalkylene group; D represents --CH₂ CH₂ -- or --O--; m represents aninteger of 1 to 40; n represents 0 or 1; and p represents O or
 1. 3. Aprocess for forming an optical sound track on a multi-layer colorphotographic material, which consists essentially of developing apicture image, and sound image exposed multilayer color photographicmaterial; applying a nitrogen containing heterocyclic compound in whichat least one of the nitrogen atoms is connected to a group having 6 ormore carbon atoms to form a quateraary salt to a sound track area of themulti-layer color photographic material; and bleaching and fixing themulti-layer color photographic material wherein said nitrogen containingheterocyclic compound is represented by the general formula: ##EQU9##wherein Z represents the atoms necessary to form a pyridine ring, animidazole ring or a quinoline ring; X⁻ represent an anion; and R₁represents a group having 6 or more carbon atoms and is selected fromthe group consisting ofa. an alkyl or an alkenyl group, ##EQU10##wherein R₂ represents an alkyl group, an alkenyl group, or an alkylarylgroup; R₃ represents a hydrogen atom or a methyl group; A represents--O--, --S--, --COO--, or --NCH₃ --; B represents --O--, --COO--,--CONH--, or --CONHC₂ H₄ CONH--; C represents an oxyalkylene group; Drepresents --CH₂ CH₂ -- or --O--; m represents an integer of 1 to 40; nrepresents O or 1; and p represents O or
 1. 4. A process for forming anoptical sound track on a multi-layer color photographic material whichconsists essentially of developing a picture image and sound imageexposed multilayer color photographic material; applying a nitrogencontaining heterocyclic compound in which at least one of the nitrogenatoms is connected to a group having 6 or more carbon atoms to form aquanternary salt to a sound track area having a silver image in themulti-layer color photographic material; and bleaching and fixing themulti-layer color photographic material wherein said nitrogen containingheterocyclic compound is represented by the general formula: ##EQU11##wherein Z represents the atoms necessary to form a pyridine ring, animidazole ring or a quinoline ring; X⁻ represent an anion; and R₁represents a group having 6 or more carbon atoms and is selected fromthe group consisting ofa. an alkyl or an alkenyl group, ##EQU12##wherein R₂ represents an alkyl group, an alkenyl group, or an alkylarylgroup; R₃ represents a hydrogen atom or a methyl group; A represents--O--, --S--, --COO--, or --NCH₃ --; B represents --O--, --COO--,--CONH--, or --CONHC₂ H₄ CONH--; C represents an oxyalkylene group; Drepresents --CH₂ CH₂ -- or --O-- ; m represents an integer of 1 to 40; nrepresents 0 or 1; and p represents 0 or
 1. 5. A process for forming anoptical sound track on a multi-layer color photographic materialconsisting essentially of developing a picture image and sound imageexposed multi-layer color photographic material; applying a nitrogencontaining heterocyclic compound in which at least one of the nitrogenatoms is connected to a group having 6 or more carbon atoms to form aquaternary salt to a sound track area of the multi-layer colorphotographic material; and bleaching the multilayer color photographicmaterial wherein said nitrogen containing heterocyclic compound isrepresented by the general formula: ##EQU13## wherein Z represents theatoms necessary to form a pyridine ring, an imidazole ring or aquinoline ring; X⁻ represent an anion; and R₁ represents a group having6 or more carbon atoms and is selected from the group consisting ofa. analkyl or an alkenyl group, ##EQU14## wherein R₂ represents an alkylgroup, an alkenyl group, or an alkylaryl group; R₃ represents a hydrogenatoms or a methyl group; A represents --O--, --S--, --COO--, or --NCH₃--; B represents --O--, --COO--, --CONH--, or --CONHC₂ H₄ CONH--; Crepresents an oxyalkylene group; D represents --CH₂ CH₂ -- or --O--; mrepresents an integer of 1 to 40; n represents 0 or 1; and p represents0 or
 1. 6. A process for forming an optical sound track on a multi-layercolor photographic material consisting essentially of developing apicture image and sound image exposed multi-layer color photographicmaterial; applying a nitrogen containing heterocyclic compound in whichat least one of the nitrogen atoms is connected to a group having 6 ormore carbon atoms to form a quaternary salt to a sound track area of themulti-layer color photographic material; and bleach-fixing themulti-layer color photographic material wherein said nitrogen containingheterocyclic compound is represented by the general formula: ##EQU15##wherein Z represents the atoms necessary to form a pyridine ring, animidazole ring or a quinoline ring; X⁻ represent an anion; and R₁represents a group having 6 or more carbon atoms and is selected fromthe group consisting ofa. an alkyl or an alkenyl group. ##EQU16##wherein R₂ represents an alkyl group, an alkenyl group, or an alkylarylgroup; R₃ represents a hydrogen atom or a methyl group; A represents--O--, --S--, --COO--, or --NCH₃ --; B represents --O--, --COO--,--CONH--, or --CONHC₂ H₄ CONH--; C represents an oxyalkylene group; Drepresents --CH₂ CH₂ -- or --O--; m represents an integer of 1to 40; nrepresents 0 or 1; and p represents 0 or
 1. 7. The process for formingan optical sound track as claimed in claim 2, wherein the bleachingagent used in said bleaching is a compound containing iron (III).
 8. Theprocess for forming an optical sound track as claimed in claim 7,wherein said iron (III) compound in ferric chloride.
 9. The process forforming an optical sound track as claimed in claim 7, wherein said iron(III) compound is an iron (III) salt of ethylenediaminetetraacetic acid.10. The process for forming an optical sound track as claimed in claim2, including exposing said multi-layer color photographiclight-sensitive material and then subjecting the color photographicmaterial to the steps of immersion in a pre-bath; color developing;stopping; silver bleach inhibiting; bleaching; fixing; and stabilizing.11. The process for forming an optical sound track as claimed in claim2, including exposing said multi-layer color photographiclight-sensitive material and then subjecting the color photographicmaterial to the steps of immersion in a pre-bath; color developing;stopping; silver bleach inhibiting; bleach-fixing; and stabilizing. 12.The process for forming an optical sound track as claimed in claim 2,including exposing said multi-layer color photographic light-sensitivematerial and then subjecting the color photographic material to thesteps of immersion in a pre-bath; color developing; stop-fixing; silverbleach inhibiting; bleaching; fixing; and stabilizing.
 13. The processfor forming an optical sound track as claimed in claim 2, includingexposing said multi-layer color photographic light-sensitive materialand then subjecting the color photographic material to the steps ofimmersion in a pre-bath; color developing; stop-fixing; silver bleachinhibiting; bleach-fixing; and stabilizing.
 14. The process for formingan optical sound track as claimed in claim 1, wherein said pyridinering, imidazole ring or quinoline ring has an alkyl group having 1 to 12carbon atoms on ring forming atoms other than the quaternary nitrogenatom.
 15. The process for forming an optical sound track as claimed inclaim 1, wherein said X is bromide, chloride, thiocyanate, sulfonate orperchlorate.
 16. The process for forming an optical sound track asclaimed in claim 2, wherein said applying comprises applying at leasttwo of said nitrogen containing heterocyclic compounds in combination.17. A process for forming an optical sound track which comprisesdeveloping an exposed multi-layer color photographic material to form apicture image and a sound image, contacting only the silver of the soundtrack area with a solution consisting essentially of a silver bleachinhibiting nitrogen containing heterocyclic compound in which at leastone of the nitrogen atoms is connected to a group having 6 or morecarbon atoms to form a quaternary salt and bleaching and fixing themulti-layer color photographic material wherein said nitrogen containingheterocyclic compound is represented by the general formula; ##EQU17##wherein Z represents the atoms necessary to form a pyridine ring, animidazole ring or quinoline ring; X⁻ represent an anion; and R₁represnets a group having 6 or more carbon atoms and is selected fromthe group consisting ofa. an alkyl or an alkenyl group, ##EQU18##wherein R₂ represents an alkyl group, an alkenyl group, or an alkylarylgroup; R₃ represents a hydrogen atom or a methyl group; A represents--O--, --S--, --COO--, or --NCH₃ --; B represents --O--, --COO--,--CONH--, or --CONHC₂ H₄ CONH--; C represents an oxyalkylene group; Drepresents --CH₂ CH₂ -- or --O--; m represents an integer of 1 to 40; nrepresents 0 or 1; and p represents 0 or
 1. 18. The process for formingan optical sound track as claimed in claim 17, wherein said solutioncontaining said heterocyclic compound is an aqueous solution.
 19. Theprocess for forming an optical sound track as claimed in claim 18,wherein said solution containing said heterocyclic compound is anaqueous methanol solution.
 20. The process for forming an optical soundtrack as claimed in claim 18, wherein said solution containing saidheterocyclic compound is an aqueous ethanol solution.
 21. The processfor forming an optical sound track as claimed in claim 18, wherein saidsolution containing said heterocyclic compound has a pH ranging fromabout 5 to
 13. 22. The process for forming an optical sound track asclaimed in claim 18, wherein said nitrogen containing heterocycliccompound is present in said solution in an amount of about 0.5 to 30weight %.